Article

From a stable silanone complex to isolable, donor-supported silicoxonium halides [LSi(dmap)=O-SiMe3](+)X-.

Technische Universität Berlin, Institute of Chemistry, Metalorganic and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Chemistry (impact factor: 5.93). 09/2011; 17(40):11274-9. DOI:10.1002/chem.201101610
Source: PubMed

ABSTRACT The first donor-stabilized silylated silicoxonium species [LSi=O-SiMe(3)](+) (L=(RN)C(=CH(2))CH=CMe(NR), R=2,6-iPr(2)C(6)H(3)) have been synthesized from the reaction of the dmap-supported (dmap=p-dimethylaminopyridine) silanone complex [LSi(dmap)=O] (1) with trimethylsilyl halides. Although the reaction with Me(3)SiCl leads directly to the Si=O addition product [LSi(Cl)OSiMe(3)] (2), the ionic silicoxonium bromide [L(dmap)Si=O-SiMe(3)](+)Br(-) (3) can be obtained as a primary product of the reaction with Me(3)SiBr, which affords [LSi(Br)OSiMe(3)] (4) with release of the dmap ligand at room temperature in THF. In the case of Me(3)SiI, the reaction furnishes the silicoxonium iodide [L(dmap)Si=O-SiMe(3)](+)I(-) (5) as the most stable species. Compounds 2-5 were isolated and fully characterized through multinuclear NMR spectroscopy, mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses.

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Keywords

dmap ligand
 
mass spectrometry
 
primary product
 
reaction furnishes
 
single-crystal X-ray diffraction analyses
 

Yun Xiong